Compositions and methods for treating hydrocarbon materials

ABSTRACT

A biodegradable, non-toxic firefighting concentrate composition. The preferred compositions include 4 to 40 parts of a C 16  -C 18  tertiary amine having 2-10 ethoxy or other solubilizing groups per mol, 1 to 15 parts of a carboxylic acid having 6 to 16 carbon atoms; 1 to 6 parts of a C 6  -C 16  alcohol and 0 to 10 parts of C 4  -and lower alcohols, and enough water to create a total of 100 parts by volume. The concentrate is usually diluted up to 100 times (v/v) with water, and is also effective when mixed with foam-forming materials. In addition, the composition is useful with soil bacteria for remediating soil contaminated with hydrocarbon fuel and for facilitating fuel dispersion and degradation within bacterial-action sewage systems.

This application is a continuation-in-part of application Ser. No.08/334,403, filed Nov. 4, 1994 now abandoned which is a division ofapplication Ser. No. 08/832,063, filed on Apr. 2, 1997, now U.S. Pat.No. 5,945,026.

BACKGROUND OF THE INVENTION

The present invention relates generally to compositions and methods fortreating fuel hydrocarbons, and more particularly, to organiccompositions having two different but functionally related end uses.

In one application, compositions made according to the invention serveto emulsify organic fuels such as gasoline, diesel fuel, kerosene,so-called jet fuel and other liquid hydrocarbons in water, thusproviding the potential for extinguishing fires and rendering masses ofthese materials non-flammable. The compositions are compatible withfoam-forming constituents to further their fire extinguishing potentialin those applications wherein foam is desired.

In another aspect, the emulsifying ability of the materials can beeffectively used to disperse concentrations of such hydrocarbonmaterials finding their way into soils and ground water to render thehydrocarbons water-transportable and readily subject to degradation bynaturally occurring and/or synthetically prepared bacteria or otheragents for degrading the hydrocarbons.

Still further, because of the wetting properties of the compositions,they can be effective as a fire extinguishing agent when the fuel is insolid form, i.e., filled natural or synthetic rubber such as is used inrubber tires or the like, and against more viscous but still flammablematerial such as lubricating oils and other heavy "cuts" of petroleum.

According to the invention, the inventive composition is able to be usedby applying it either to surface or subsurface concentrations ofhazardous or undesirable hydrocarbons, including masses of gasoline, oiland the like that are spilled on land, and which are intentionally orunintentionally disposed of in sewers, exposed to the soil or the air,or otherwise as the result of an accident of some sort. Chemicalbreakdown of the dispersed hydrocarbons can be accelerated by increasingthe concentration of available bacteria for this purpose. In some cases,the surface active agent ("surfactant") composition itself can serve asa nutrient for the bacteria, thus enhancing its action in degrading thehydrocarbon materials.

In the past, the concept of utilizing surface active agents in water fortreating fires has often been suggested. One aspect of the use ofsurfactants in firefighting is that such treatment can render the water"wetter," i.e., better able to penetrate into and through the surfacesof semi-solid materials.

Moreover, the ability of surfactant materials to create frothing orfoaming has been used in an attempt to provide a barrier at theliquid-air interface, which barrier will block oxygen from access tovapor at the liquid surface, usually the surface of a mass of burningoil or gasoline. In this connection, it is well known that, particularlyin a petroleum-based fire, the combustion occurs only in the vaporphase, wherein oxygen in large quantities is readily available to thevapors originating within the liquid. In a fire, the increase intemperature accelerates the liquid vaporation and hence the rate ofcombustion. In many instances, surface active agents, particularly whenaccompanied by agitation, serve to achieve a mix of liquid water andfuel, thus rendering the fuel less volatile and less susceptible toburning. However, prior approaches to formulating compositions for thispurpose have been accompanied by a number of drawbacks, as referred toelsewhere herein.

Referring to another aspect of treating petroleum or like materialsfollowing an accident or disaster of some sort, such as an oil spill onland or at sea, the advantage has been taken of the ability ofsurfactants to disperse oils in water. However, in many cases, thesurfactants used introduce drawbacks which partially or completelyoffset the advantages sought to be gained by their use. Thus, in manycases, surfactants were effective to reduce the surface tension betweenthe oil and the water, causing the oil to spread out and form anexceptionally thin film on the surface of the water. While this maydecrease the concentration of oil in a particular area, it was laterdiscovered that it results in extremely adverse effects on marinewildlife. In one aspect, it was found that surfactant treatment exposedwildlife to smaller but still damaging amounts of oil over areas thatwere increased from a few square yards or acres to areas of many acresor even many square miles. In the case of large ocean oil spills,hundreds or thousands of square miles can be actually affected by a thinfilm of oil.

A number of other drawbacks and disadvantages also characterized theprior art use of surfactants in attempting to contain the ill effects ofoil spills or the like. In some cases, the chemical nature of thesurfactant, particularly the oleophilic portion of the surfactant, wasitself hazardous or undesirable from an ecological standpoint. Thus, anumber of years ago, it was determined that the simple matter of washingoily substances with certain surfactants would be effective to dispersethe oil in surrounding water, but it was also found that the surfactantitself was highly persistent and resistant to biological degradation.For example, the use of many surfactants made from highly alkylatedcyclopentanes was curtailed, but only when this adverse side effect wasdiscovered.

Another dilemma that has faced workers dealing with oil and gasolinespills, for example, involves attempts to remove the offending materialfrom streets, sidewalks, and lawns, for example, by introducing theminto the sewer system. However, it is well accepted that such materials,as presented to the sewage system, are resistant to degradation byresident bacteria in the sewage treatment plants. This being the case,it is apparent that such oily materials are effectively even moreresistant to degradation by the much lower concentrations of bacterianaturally occurring in the soil.

Referring to such disposal of petroleum wastes in sewers, this has beendiscouraged or legislated against because of the persistent nature ofthe oils and the like, and their long-term resistance to degradation. Inextreme cases, oily residues washed into a sewer system can impede theintended operations of a sewage system as well as stubbornly resistingdegradation of the contaminants themselves. Consequently, addressing oilspill problems has been difficult and problematical. If allowed toremain untreated, a fire or soil contamination hazard persists, and iftreated with the wrong materials, alternative and sometimes equallyundesirable hazards can be created.

Still further, while it has been suggested that for each individual oilspill or the like, cleanup workers might find a particularly suitableagent for the job, this is not really helpful. This is because suchcleanup or firefighting personnel may not know in advance whether themajor hazard is an existing fire, a potential fire, soil contamination,sewage system contamination, or emission of harmful vapors. Thus, it isnot practical for emergency crews to be fully stocked with everypossible type of chemical agent that might be useful when responding toan emergency.

Under these circumstances, it would be considered very advantageous if asingle composition could be provided that would have excellent successwhen used as an addition to water for firefighting purposes, and whichwould not create undesirable side effects.

It would also be highly advantageous if there were a waterbornecomposition which could be used against bodies of hazardous waste suchas petroleum spills and the like, and which would render themnon-flammable as well as non-objectionably dispersible in ground water.In this connection, it will be understood that a main difficulty withmany petroleum-based hazardous wastes is not so much that they never canbe attacked by bacteria, but simply the extremely long time it takes forthem to be degraded by soil bacteria in the form of naturally occurringmicroflora and microfauna.

In this connection, it will be understood that many hazardous waste,particularly petroleum wastes, are extremely insoluble in water and thustend to stay in the soil near the spill area. It is believed that suchmaterials are strongly absorbed onto the non-aqueous components of thesoil and remain relatively safe from bacterial degradation for tworeasons. One is that they are highly concentrated, and the other is thatmost bacteria are water-borne or tend to thrive in aqueous environments.

Such bacteria being effective roughly in proportion to theirconcentration, many bacteria are simply not sufficiently concentrated todegrade large, monolithic petroleum spills within a finite time,especially where the surface-to-volume area of such oily materials islow and the supply of bacteria is also low.

On the other hand, when very finely dispersed, such as by a highlyeffective surfactant, such materials may be destroyed much more quicklyby bacteria, including those which may be naturally occurring, or thosewhich may be supplied to the spill site for this purpose. A mixture ofboth types can also be used.

Thus, if it were possible to disperse oily materials into sufficientlyfine particle sizes and reduce their strong absorption on soil, suchmaterials could then be entrained in the aquifer. Once so dispersed, theoily materials could be biodegraded by water-borne bacteria within areasonable time. In addition, or in the alternative, the water with thedispersed oils in it could be dealt with by "pump and treat" technology.In the latter connection, it has been found that while such "pump andtreat" methods may be effective, their effectiveness depends on theassumption that the material to be treated is a waterborne material. Inmany cases, this is not functionally true in the sense that, while somematerials are waterborne, there are other materials remaining in thesoil which only become waterborne after the lapse of months or years,thus almost indefinitely prolonging the "pump and treat" period.

Referring again to prior practices, several attempts to achieve adispersion of oily materials in water have been unsuccessful because thesurfactants in effect increase the toxicity of the oil relative toaquatic life. In particular, many surfactants render the cell walls ofanimal and plant life more permeable to biological hazards, thusincreasing the effective toxicity of certain materials to such marinelife. This usually occurs with a surfactant where the oleophilic portionof the molecule is synthetic rather than naturally occurring.

Referring again to bacterial treatment, it would be further advantageousif the surfactant used would also serve as nourishment for the bacteriaor make nourishment available from the substrate. It would also beadvantageous if a composition of surfactants and other materials couldfill the above requirements and also be compatible with foam-formingconstituents.

In view of the failure of the prior art to provide a chemicalcomposition for treatment in emulsifying petroleum presenting a fire orspill hazard, it is an object of the invention to provide an improvedcomposition for such purpose.

Another object of the invention is to provide a composition whichincludes surfactants and other components which are essentiallynon-toxic, even when used in substantial concentrations.

A further object of the invention is to provide a composition which maybe used to treat water used in dispersing petroleum and like wastes inwater so as to lower the vapor pressure of such water and expose them tobacterial action.

A still further object of the invention is to provide a compositionwhich, when added to water used to treat petroleum or otherhydrocarbons, will free adsorbed hydrocarbons from the soil and convertthem into waterborne materials of greatly reduced particle size, able tobe degraded by naturally occurring or specially supplied or augmentedbacteria.

Yet another object of the invention is to provide a treating compositionfor water which is usable in a variety of emergency response situations,including petroleum firefighting, and in treating water- and landbornepetroleum spills and the like.

Another object is to provide a composition for treatment of petroleumwhich will render limited amounts of spilled petroleum compatible withsewage systems.

A further object of the invention is to provide a composition forfirefighting which includes an especially effective surfactant actionand further provide a foaming action and in which the surfactantcomponent for dispersing oil in water is compatible with a stable, highdensity foam.

A still further object of the invention is to provide a method oftreating petroleum to render it non-flammable and dispersible in such away as to render it susceptible to bacterial attack.

Yet another object of the invention is to provide a method of soiltreatment or remediation wherein contaminated soil may be treated by amix containing specially blended surfactants that are able to renderpetroleum oils dispersible in ground water and able to be attacked bybacteria including bacteria supplied for the purpose of soilremediation.

Another object of the invention is to provide a chemical compositionwhich is effective to disperse petroleum in such a way that the oil willassume extremely fine particle size and wherein the surfactant is notharmful to aquatic animal and vegetal life.

A further object of the invention is to provide a treating compositionfor petroleum which includes a surfactant made from an animal tallowmodified by chemical treatments including ethoxylation and which furtherincludes selected alcohols and organic carboxylic acids, rendering themixture dispersible in water and providing a strong emulsifying actionfor petroleum based fuels and lubricants.

A still further object of the invention is to provide a chemical mixturewhich is non-harmful to naturally occurring plant and animal life, evenwhen applied to or mixed with petroleum products.

The foregoing and other objects and advantages of the invention areachieved in practice by providing a chemical composition including fromabout 7 to about 40 parts of an ethoxylated tallow amine, about 1/2 to15 parts of alcohols of low and medium molecular weights and up to about25 parts of an organic carboxylic acid, with the remainder being water,such that 100 parts are present in the entire composition, with acomposition preferably including a preservative and a high visibilitydye. The invention also achieves its objects by using a method whichincludes using the above mixture to disperse oil in water used toextinguish fires, or used to disperse oil spilled on land or water forattack by naturally occurring or added bacteria present in the soil orin waste disposal systems.

The exact manner in which the foregoing and other objects and advantagesof the invention are achieved in practice will become more clearlyapparent when reference is made to the following examples of practicingthe invention set forth by way of illustration, and the discussionregarding such exemplary products, mixtures and methods.

DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

The present invention may be embodied in different forms and theformulations and methods referred to herein are capable of being variedwithin certain ranges. Accordingly, several working examples of themanner in which the invention may be practiced can be determined fromthe following examples set forth by way of illustration only and not byway of limitation.

EXAMPLE 1

The following constituents were prepared and mixed in the followingproportions by weight:

    ______________________________________                                        tallow amine-5 mols ethylene oxide (avg)                                                                12.5 parts                                            isononanoic acid   8.0 parts                                                  n-octanol/n-decanol in 50/50 mixture   2.5 parts                              cranberry dye  900 ppm                                                        isopropyl alcohol   4 parts                                                   water (about 73 parts) sufficient to make                                      100 parts total.                                                           ______________________________________                                    

To prepare the above mixture, a mixing tank of suitable size is providedand water is added in the above amount. Next, the preservative is addedto prevent against bacterial, yeast, or like contamination. Dyesufficient to create a highly visible red color is pre-dissolved in asmall amount of water with agitation for four minutes. Next, theisopropyl alcohol is added to the mixing tank and agitated for a periodof three to four minutes, after which the pre-mixed dye solution isadded and an additional four minutes of mixing are carried out. Next,the tallow amine surfactant is blended into the water with the dye, theisopropyl alcohol and the preservative. Finally, the isononanoic acidand the 50/50 octanol/decanol mixture is added. A strong agitatingaction is continued to avoid gelling the product, which then comprises aviscous liquid with a brilliant red color.

Having mixed the composition as just described, a specimen petroleumfire was initiated in keeping with an accepted test procedure. This fireis prepared by using a pit which is 80 feet in diameter and has a depthof 3 feet, with a concrete bottom. The pit is filled with water to adepth of about two feet, and a 250 gallon liquid mixture of gasoline anddiesel fuel is pumped onto the surface of the water, where the volatilehydrocarbons form a floating layer. The petroleum layer is ignited andpermitted to burn for three minutes, emitting a dense, billowing cloudof black smoke. A water pump capable of delivering 100 gpm was actuatedand the additive was injected into the water stream downstream of thepump on the basis of 3% of the additive by volume in relation to thewater. Upon initial application of the water stream to the burning poolof liquid hydrocarbon, the dark black smoke immediately became a muchless dense gray smoke and the fire was extinguished almost immediately.Attempts to reignite the fire after a period of several minutes andone-half hour were equally unsuccessful. Observation showed that thewater and petroleum were clearly emulsified presenting a surface layerhaving a cloudy, milky appearance. The odor of volatile petroleum wasabsent and the resulting mixture resisted further attempts at lighting.

From the above, it was concluded that the water treated with the abovecomposition was highly effective at extinguishing a fire within anextremely short time. The residue from this attempt was labeled as"treated petroleum--1" and was retained for subsequent analysis.

EXAMPLE 2

A mixture as described was prepared as described above and an identicaltest was performed, differing from the prior test only in that thepercentage of surfactant mixture added to the water supplied by the pumpwas in the amount of 6% by volume relative to the water. The resultswere substantially similar to those of Example 1 except that the firewas extinguished even more quickly. The emulsification action wasthorough and complete. The material resulting from this experiment wasreferred to as "treated petroleum--2" and retained for analysis.

Regarding the test performed in the Examples 1 and 2, the emulsionproduced appeared to be stable and no phase separation was observed evenafter a period of several hours. Hence, it was concluded that the fireextinguishing treatment using either of the methods just described wouldbe effective not only to rapidly extinguish the fire, and abate thesmoke, but also to render the material resulting from the treatmentnon-flammable, so as to eliminate any hazard of re-ignition, a commonrisk with oil and gas fires.

EXAMPLE 3

Next, an identical test was performed using the same material andapplying it to the same sort of fire in the same way, except that thesurfactant concentrate in water solution was applied in the proportionof 2% concentrate in relation to the water. While the rate of smokeabatement and fire extinguishing was slightly slower, the process wasnevertheless highly effective to abate the smoke and extinguish thefire. The performance of the emulsion was substantially the same in thatthere was no phase separation, and no floating or supernatanthydrocarbon layer appeared, even after several hours. This materialcomprising the fuel and the extinguisher composition and water waslabeled--"heated petroleum--3."

From the foregoing, it was concluded that the concentrate was effectivein proportions up to 6% by volume in relation to the applied water, andthe active ingredients were present in the concentrate in amounts aslittle as 20% or less. Subsequent tests proved that volume percentagesof concentrate to applied water could be effective at levels as low as1% to 11/2% by volume. These refer to the level of concentrate, with thesurfactant level being correspondingly lower.

In the above examples, the product referred to as "tallow amine--5 molsethylene oxide" is essentially an ethoxylated tertiary amine. Theproduct is believed to be prepared by using as a starting material ananimal tallow, known to be a triglyceride of C₁₆ -C₁₈ fatty acids. Afterrendering the tallow to create the individual fatty acids, the resultingacids are reacted with ammonia to create a fatty acid amide.Subsequently, the amides so prepared are dehydrogenated to formnitrites. Thereafter, the nitrites are rehydrogenated to form amines, inthis case a primary fatty amine. Subsequent ethoxylation of the twoactive hydrogen atoms on the amine groups using ethylene oxide createsan ethoxylated C₁₆ -C₁₈ amine preferably having 1 to 4 ethoxy groupsreplacing each hydrogen. The tallow amine proven most successful withthe present invention carries an average of five mols of ethylene oxideper amine molecule. In such compositions, a number of isomers arecreated, with 1 to 4 ethylene oxide groups replacing each of thehydrogen atoms and the balance of the five mols being present at theother position. Schematically, such composition may be represented asfollows: ##STR1##

One isomer might be represented as follows: ##STR2##

Because the five mols of ETOH is an average number in the aboveschematic, the number of ETOH groups on any one molecule maysignificantly exceed a total of five, i.e., there may be fewer than fiveor up to ten or more groups on any one individual molecule. Thus, thecomposition is usually to be thought of as a series of homologs and/orisomers. Similar ethoxylated amines derived from homologs of the animaltallow-based products may also be used in keeping with the invention.

Regarding the characterization of the above surfactant, in somerespects, the ethoxylated amine may be considered a non-ionic surfactantin that it is not readily ionizable in water. However, in the presenceof lower molecular weight organic acids, such as formic and acetic acid,the surfactant may be protonated so as to take on the characteristic ofor resemble a cationic surfactant. In the presence of higher or mediumweight carboxylic acids, such as the fatty acids, the surfactant acts asa non-ionic surfactant.

The above isononanoic acid is a C₉ carboxylic acid, that is believed toexist in a number of C₉ isomers; hence, it is also generically known astrimethylhexanoic acid. It is an aliphatic carboxylic acid having aboiling point of about 235° C. at 1,000 mb. The acid is slightly solublein water and has a pH of about 3.5 at that concentration.

The higher alcohol mixture, i.e., the n-octanol/n-decanol mixturereferred to above is preferably about an even or "50/50" mixture of thetwo alcohols, although a 45/55 mixture has been used successfully.

The preservative used is preferably a solution of sodium di-2-ethylhexylsulfosuccinate. This composition is identified by code number 3409 inthe Merck Index. Preferably, a dipropylene glycol/sodium hydroxidesolution is used with the preservative to impart solubility and topromote hyrolysis of the sulfonate salt, as is known to those skilled inthe art.

Referring to the cranberry dye, its purpose is to facilitate adjustmentof the concentration of the concentrate in water being sprayed. Astrong, highly visible dye permits the concentration of the additive inwater to be controlled by visual observation and adjustment relative toa visual standard.

EXAMPLE 4

A composition as set forth above was provided except that the tallowamine-ethylene oxide concentration was reduced to 8 pph (parts perhundred) in relation to the composition as a whole. Thetrimethylhexanoic acid concentration was reduced to 4.5 pph and the C₈-C₉ alcohol mixture to about 1%. The isopropyl alcohol was reduced toabout 1/2 pph, and the balance was water. In this instance, the waterapproximated 85-86% of the overall composition. The product waseffective in rapidly extinguishing a fire when used in concentrations ofbetween 1% and 6% relative to the firefighting water.

EXAMPLE 5

In this instance, the ethoxylated tallow amine concentration was raisedto 38 pph and the C₉ acid to 25 pph. The C₈ -C₁₀ alcohols were presentat just over 11 pph, and the isopropyl alcohol was present in the amountof 6 pph. In this instance, about 25 pph of water were present. Whilethis mixture is very viscous and requires care in mixing, when dilutedin the above ranges and applied to a test fire, it was also foundeffective to rapidly emulsify and disperse the hydrocarbon fuels, thusrapidly extinguishing the fire and leaving a non-flammable residue.

EXAMPLE 6

A similar composition was made using approximately 20 pph of the tallowamine-ethylene oxide, 15 pph of the acid, 5 pph of the C₈ -C₁₀ alcoholand 4 parts of isopropyl alcohol, with the balance (about 66 parts)being water. This product proved highly satisfactory at all of thevarious dilution rates referred to above.

EXAMPLE 7

A composition was prepared as in Example 1 except that the C₉ acid wasreplaced with a C₈ acid, 2-ethyl caprylic acid, also known as 2-ethylhexanoic acid. While a composition made in this manner was notnecessarily preferred as the best presently constituted formulation, itwas nonetheless very effective. The C₈ acid may, in some circumstances,prove less irritating to human skin and hence more desirable from ahandling, manufacturing and/or labeling standpoint than the C₉ acid.However, neither of the acids provided an objectionable residue whenused as described herein.

EXAMPLE 8

A firefighting composition was prepared in keeping with Example 1 exceptthat the isopropyl alcohol was eliminated entirely. It was determinedthat, although mixing was rendered somewhat more difficult, it waspossible under some conditions to obtain a dispersion of all theingredients without using any lower aliphatic alcohol. This establishedthat the lower alcohol was not essential, although it was preferred forease of mixing. Omitting the alcohol may provide some administrativeadvantages in that compositions containing such alcohols have morestringent labeling requirements than those without the alcohols. Aconcentrate of this composition was effective to extinguish fires atfrom between about 1% to 6% or more by volume in water.

EXAMPLE 8A

A firefighting concentrate composition is prepared by mixing variousingredients to form a surfactant concentrate, following which thesurfactant concentrate is mixed with a water-biocide solution to form afirefighting concentrate. Finally, this firefighting concentrate as thusprepared is dyed to form a dyed firefighting concentrate. The dyeassists users in determining the extent to which the firefightingconcentrate should be diluted in water for use as a concentrate-treatedfirefighting water.

The surfactant concentrate is prepared by mixing a surfactant, an acidand an alcohol, in the proportions identified below:

    ______________________________________                                        Surfactant component:                                                           ethoyxlated amine derived from 375 gallons                                    animal tallow (avg. 5 mols                                                    ethylene oxide per molecule)                                                  Acid component:                                                               carboxylic acid 227 gallons                                                   (2-ethylhexanoic acid)                                                        Alcohol component:                                                            decanol (55+%) octanol (43+%)  70 gallons                                     ethyl-1-hexanol (1%)                                                        ______________________________________                                    

The foregoing ingredients are thoroughly mixed, preferably at or aboveroom temperature, in a mixing vessel of suitable size, to form asurfactant concentrate. This concentrate has a medium, honey color, andwill have a specific gravity of 0.94-0.95, a pH of 5.7-6.5 and aviscosity (#2 Zahn Cup) of 62-66.

Next, a diluting mixture was prepared by adding 2.5 gallons of asuitable biocide ("PROXEL 6XL") to 1,728 gallons of water. Thesurfactant concentrate is added to the above diluting mixture, and mixedthoroughly (15-30 min.) following which about 2.5 gallons of an intensered dye ("16878 AUTOMATE RED B") are added. This concentrate has aspecific gravity of 1.00-1.01, a pH of 5.7-6.5 and a viscosity (#2 ZahnCup) of 38-42. This firefighting concentrate is suitable for injectioninto firefighting water in amounts of from about 0.5% to about 6% ormore, preferably 2%-3%. The performance of the treated water isexcellent, demonstrating rapid fire extinguishing capabilities.

In the above composition of Example 8A, the preferred form of surfactantcomponent may be partially or fully replaced by surfactants of the typedescribed in the discussion above following Example 3. The acidcomponent may be the above-identified acid, an acid such as theisononanoic acid referred to in Example 1, or equivalent. The alcoholcomponent may be higher or lower homologs of the listed materials, andthe mix of alcohols may vary significantly from the approximately 50/50mixtures referred to in Example 1.

The lower (isopropyl) alcohol which was listed as being optional inExample 1 is not necessary in the composition of Example 8A, but mSghtbe added if desired.

SUMMARY OF THE ABOVE EXAMPLES

In the foregoing Examples 1-8 illustrate the variety of proportions inwhich the ingredients are effective. Based on tests performed in pursuitof analyzing various formulas, the following range of proportions may beused in providing additive compositions which will be effective inachieving the objects of the invention.

    ______________________________________                                        ethoxylated tallow amine (avg. 5 mols                                                                5-40    parts                                            ethylene oxide) or similar tertiary                                           amine-type surfactant                                                         isononanoic acid (trimethyl hexanoic 2-12 parts                               acid) or other suitable acid                                                  n-octanol/n-decanol mixture (approx. 1-5 parts                                50% ea.) or similar alcohol or alcohol                                        mix                                                                           preservative 1200 ppm                                                         cranberry or AUTOMATE RED B dye 900 ppm                                       isopropyl alcohol (optional) 0-8 parts                                      water                  balanced to 100                                           parts total.                                                               ______________________________________                                    

In any of the above examples, a substitution of the C₈ acid referred toin Example 7 may be made for the C₉ acid, and a substitution of theethoxylated coconut amine may be made for the ethoxylated tallow amine.The percentage of octanol and decanol in the above mixture may also bevaried in ranges of from about 4 to 1 to about 1 to 4.

EXAMPLE 9

This example relates to the use of a composition of the type set forthin Examples 1-8 wherein, for various reasons, it may be desirable notonly to emulsify the hydrocarbon supplying fuel to the fire, but also toprovide a blanket of foam over the burning area. For this purpose, it ispossible to add to the compositions of Examples 1-8 additionalingredients for the purpose of making a frothy, highly stable foam.

Preparation of a modified concentrate is as follows:

    ______________________________________                                        Ingredients per Example 1                                                                               100 parts                                             Polyoxyethylene coconut amine  7.68 parts                                     Coco-dimethylamidopropyl betaine  1.45 parts                                  Sodium di-2-ethylhexyl sulfosuccinate  1.45 parts                             Fatty amide cationic surfactant  1.45 parts                                   Total 112.03                                                                ______________________________________                                    

When a froth is created by mixing the above composition with the waterunder turbulent conditions, a highly stable foam will result. Thus, thisconcentrate was injected into a stream of water at a volumetric ratio of1 part per hundred. In a test fire, water treated with the concentratealso proved highly effective, "knocking down" the fire and extinguishingit without leaving a flammable residue for potential re-ignition. Thetest fire was blanketed with a stable layer of foam which remained inplace and was visible atop the pool of emulsified water and fuel. Thus,the composition of the invention appears compatible with foam-formingingredients of the type described herein and is equally or perhaps moreeffective in firefighting when used with such supplemental materials.

In formulating this composition, the preferred order of addition is toprovide a necessary water, and add the biocide and the dye thereto.Thereafter, the mixture of higher aliphatic alcohols (octanol/decanol)or their homologs are stirred into the mixture. Next, the aliphaticacid, in this case, 2-ethyl hexanoic acid is added. Thereafter, thecoconut amine is added, following which the coco-dimethylamidopropylbetaine is added. Next, the fatty amide surfactant is added to themixture and finally, the ethoxylated tallow amine component is stirredin. If a lower alcohol (C₂ -C₅) is used, it may be added at this point.

Once the composition just described was mixed, a fire of the typedescribed herein was prepared, and the composition of the invention wassprayed over the fire using the same equipment and at the same ratedescribed in connection with Example 1. The fire was promptlyextinguished and a high, persistent blanket of foam covered the test pitarea. Study of the fire pit area revealed that the blanket of foamremained atop the liquid material, but the emulsifying or dispersingcomponents of the firefighting composition worked to disperse the liquidfuel in the subnatant water layer. Accordingly, it was shown that whilethe covering foam and the extinguishing composition serving to dispersethe flammable liquid within water were both applied together, eachappeared to function separately in that the foam blanket remained atopthe liquid phase while the dispersant composition was not retainedwithin the foam layer but was free to contact the fuel/water layer andultimately achieve the intimate mixing, dispersion or emulsificationnecessary to inhibit any restart of the fire, and render the hydrocarbonfuel non-volatile.

In contrast to the composition of the present invention, many of themost commonly used fire extinguishing agents, namely, most aqueousfilm-forming foams (AFFF) used to extinguish burning organic liquids areconsidered hazardous materials and have a finite shelf life.Accordingly, the materials are hazardous, and furthermore, theirdisposal also creates a hazardous waste problem. Unlike AFFF, thepresent compositions do not possess shortened shelf lives and are notthemselves hazardous so as to require periodic disposition. Even ifdisposed of, they do not create forbidden hazards. While some foams havebeen described as being non-toxic, most or all of those presently inwidespread use are known to be hazardous.

EXAMPLE 10

A concentrate composition was made according to Example 9, except that,when used to treat the same test fire, the concentrate was used at avolumetric ratio of 3 parts per hundred of treating water. The testresults were satisfactory and perhaps achieved slightly fasterextinguishing of the fire in relation to water having a reducedpercentage of concentrate.

EXAMPLE 11

A composition according to Example 9 was prepared as stated therein, andin this example, the concentrate was injected into a stream of fireextinguishing water at a volumetric ratio of 6 parts per hundred. Thefire and other conditions were identical, and this concentration of thecomposition provided slightly improved extinguishing qualities in termsof time response. Thus, Examples 9-11 demonstrate that concentration mayvary from about 1 part or less to 6 parts of more of concentrate perhundred parts of water without compromising the effectiveness of theconcentrate.

Additional Examples

The following examples relate to hazardous situations that are commonlyencountered, other than fires, but in which the hazards may be protectedagainst using the inventive compositions. The risks held out, and themanner in which they are assessed and treated will now be discussed.

In many commonly occurring situations, fuel oil or the like is spilledin an area where it creates an immediate fire hazard. Applying thecomposition comprising the concentrate of the invention and a mass ofwater immediately eliminates the fire hazard. However, because theresulting treated fuel material may have what may be thought of as threepossible destinations, one of three situations arises. The hydrocarbonfuel, in the event of being spilled on a waterway, from a boat or slip,for example, would directly enter a river or stream. Fuel may also entera waterway where the spill involving a road vehicle occurs on a road inthe vicinity of a river crossed by a bridge, into a river or creekadjacent the roadway. In such cases, the spilled petroleum and thetreating material would be waterborne from the outset.

In another circumstance, the spill might be transferred to the soil,directly or indirectly, and the soil, while able to contain moisture,would be a primarily solid phase area rather than a liquid phase region.Contaminants, if not treated, would linger in the soil and eventuallyenter the ground water system. Most such spills come from vehicles,storage tanks or pipelines.

In the third common situation, the spill would occasion cleanup effortsdirected at causing the spilled material to enter a sewage disposalsystem where sewage sludge is used for degradation. In the respectivecases just discussed, the risks are primarily those of immediatelycontaminating the water in a waterway, contaminating the soil andeventually ground water, and finally, interfering with or reducing theeffectiveness of sewage treatment. The greater the extent of the spill,if not treated, the more severe is the problem. In many cases, if thespill is not treated properly, the effects of the spill and/or thetreatment can be relatively persistent as well as widespread.

Accordingly, the examples set out below are directed to illustrations ofthe effectiveness of the product involving respective spills of thekinds just discussed.

Referring now to various tests and simulations used to demonstrate theadvantages of the invention in these situations, certain tests can bemade for toxicity, and some for biodegradability. One such testprocedure is known as a 96-hour acute toxicity test using a fish speciesidentified as fundulus heteroclitus (the mummichog or killifish). Thistest is used to evaluate toxicity risks involving marine line existingin a medium (water) wherein the hazard arises from soluble toxins. Othertests involve using delicate invertebrates such as Daphnia magna (waterflea), Hyalella azteca (an amphipod). Other fish used in toxicity testsinclude the Pimephales promelas (a fathead minnow). Other tests notdirected to toxicity per se involve adsorption on columns of soil,followed by elutriation. The effectiveness of emulsification can bedetermined by comparing vapor pressure of the fuel before and aftertreatment.

Other tests involve biodegradability, which can be established throughvarious tests and observations. In determining the nature and extent ofbiodegradability and the nature of the reactions between the variousdispersant materials with which the invention is concerned and thecombination of such material with fuels in water, and the degradation ofsuch materials in the presence of bacteria or activated sludge, accountis taken of several factors. These include the chemical oxygen demand(COD), the biochemical oxygen demand (BOD), the dissolved oxygen (DO) inthe water, and the oxygen uptake rate (OUR).

Regarding another aspect of the biodegradability of the composition, thealcohols and carboxylic acids were, and are known to be, readilyattacked by bacteria and degraded. In the surfactant composition, theoleophilic portion is based purely on animal fat and hence is readilybiodegradable. The ethoxy substituents are also biodegradable. Thus, thecomposition as a whole is clearly biodegradable in keeping with acceptedprotocols.

EXAMPLES 12-14

The specimens of treated petroleum ("treated petroleum--1", "treatedpetroleum--2", and "treated petroleum--3") referred to in Examples 1-3above, were tested for toxicity in comparison to hydrocarbon fuel(diesel oil). The specimens, which comprised an emulsified form of thepetroleum making up the spill (diesel fuel), displayed no toxicity otherthan that attributed to diesel fuel itself, and thus demonstrated thatthe product, even when added to petroleum spills, does not harm theenvironment.

EXAMPLE 15

Example 15 involves so-called bio-remediation, one phase of whichincludes the removal of non-aqueous phase liquids (NAPLs) from surfaceand ground waters. In keeping with the invention, a test was conductedwherein a sample of #2 diesel fuel was placed in water and treated withthe concentrate composition of the type described in Example 1,dispersed in water on the basis of 1%-10% by volume, and observed overan extended time. It was shown that the diesel fuel was attacked andbroken down into soluble, non-toxic products by bacterial action. Therelatively high rate of breakdown was attributed to the dispersion ofthe fuel and the great increase in its surface-to-volume ratio.

EXAMPLE 16

Example 16 also involves bio-remediation. Effectiveness of the treatingcomposition was demonstrated using a test wherein, after diesel fuel wasspilled on test soil, the soil was treated with a composition such asthat referred to in Example 15, above. The composition containing theemulsifying and dispersing concentrate attacked and dispersed the fuel,with the resultant product working its way into the soil over a periodof time. After such a time period, soil sampling and/or laboratory testsreveal that the emulsified and dispersed petroleum had been attacked bysoil bacteria that were dispersing degrading the fuel material.

In addition, it was observed that the constituents of the surfactantportion of the emulsifying and dispersing concentrate were themselvesalso serving as nutrients for the bacteria. Consequently, bacterialmultiplication and degradation of the fuel oil as well as theemulsifiers continued with the result that the soil contaminationeffectively disappeared over a satisfactory period of time.

EXAMPLE 17

This example also relates to so-called bio-remediation where soil iscontaminated by hydrocarbon fuel. Using the same dispersed concentrateand contaminated test soil as in Example 16, the same procedure wasfollowed, except that, after application of the dispersed concentrate,additional water-borne bacteria were added to the soil. These bacteriaessentially replicated naturally occurring bacteria compatible withsoil, but effectively provided a greatly increased concentration ofbacteria.

The fuel oil was dispersed by the concentrate and then was digested anddecomposed into soluble components much more rapidly than without theaddition of bacteria. As pointed out in the introduction, microbialattack on most hydrophobic contaminants, including hydrocarbon fuels andlubricants, is extremely slow because of the low solubility of thecontaminants in water. As is well known, many materials that areinsoluble in water or aqueous solutions tend to be adsorbed onto thesurface of water-insoluble materials and thus resist dispersion orsolution in water. Accordingly, high molecular weight, non-polar oilymaterials such as petroleum or other hydrocarbons used as fuel or inindustrial processes have a natural affinity for the hydrophobicportions of soils.

According to the present invention, the fine dispersion of spilledhydrocarbon fuels and other materials able to be achieved by the use ofthe inventive compositions serves to accelerate greatly theirdegradation by existing soil microbes. Moreover, compositions such asthose set out in Example 1 are highly useful with contaminated soils towhich additional bacteria are added in order to speed up the attack onthe offending hydrocarbon materials. Thus, the mechanism appears to bethat when the effective concentration of bacteria is greatly increasedby supplementing natural bacteria with additional bacteria, and when theaccessibility of the treated material to bacteria is greatly increasedbecause of a great increase in surface-to-volume ratio of the spilledmaterial, thus presenting an immense water/hydrocarbon interface area,bacteria will begin and continue to attack the contaminants at a highrate.

In addition, the surfactants themselves serve as nutrients for thebacteria to continue the degrading action.

EXAMPLE 18

In this example, a test spill involving diesel fuel was treated with aemulsifying concentrate of the types described in the examples herein,dispersed in water at a volume dilution of 1% up to 10% The test spillmaterial was flushed into a sewage treatment system that involvedcollection and treatment using sewage sludge, preferably activatedsludge.

The tests and demonstrations involved in adding the dispersingcomposition to such spills for ultimate treatment by sewage demonstratedthat the principal drawbacks of sewage treatment of hydrocarbon fuelspills was overcome by the composition of the invention. These drawbacksbasically comprise the general resistance to degradation of thehydrocarbon fuel when it is untreated and secondly relate to thecovering of sludge with an oily coating, rendering it unable to performits intended degradation of sewage materials generally.

Thus, in the prior art, a petroleum spill could compromise theeffectiveness of sewage treatment as well as fail to be degraded by thematerial. The concentrate of the invention, even when dispersed in largevolumes of water, was able to overcome these drawbacks. Treatedpetroleum was readily digested by the sewage sludge, including activatedsludge within a satisfactory time period. Moreover, the fine dispersionof the fuel left major portions of the surface open and available fortreatment of the surrounding sludge. Hence, the composition rendered thepetroleum fuel compatible with accepted sewage treatments. This in turnenabled petroleum hydrocarbons to be disposed of by washing and entryinto municipal sewer systems without undue damage.

Summary of Advantages

From the foregoing tests and examples, it is apparent that thecompositions of the invention, in contrast to certain known compositionsintended for the same ultimate purpose, have the advantages ofbiodegradability, and non-toxicity, enabling them to be used in manyapplications wherein other such compositions would not be acceptable. Asthe result of their biodegradability, a cleanup would not be requiredafter the application results in extinguishing a fire, with portions ofthe unburned or residual spill being not requiring expensive cleanup. Infirefighting performance, so-called "flashback" is prevented by theability of the composition to emulsify so-called Class B flammableliquids. The composition has proven effective on both Class A and ClassB fires. In contrast to the use of AFFF, the composition of theinvention is not limited by concerns about breaking or opening the foamblanket created by application of AFFF. Consequently, more aggressivefirefighting techniques, i.e., more intense agitation of the liquidsurface and use of high application rates may be employed to reduce thepotential for re-ignition of an existing fire.

It will thus be seen that the present invention provides several novelcompositions and methods for treating hydrocarbon materials, suchmethods and compositions having a number of advantages andcharacteristics, including those expressly pointed out here, and otherswhich are inherent in the invention. Various illustrative embodiments ofthe product of the invention having been shown and described by way ofexample, it is anticipated that variations to the described compositionsand methods will occur to those skilled in the art and that suchmodifications and changes may be made without departing from the spiritof the invention, or the scope of the appended claims.

What is claimed is:
 1. A method of remediating a naturally existing soilhaving therein water sufficient to support plant life and aquatic flora,said soil further including naturally occurring soil bacteria, whereinsaid soil is contaminated by hydrocarbon fuel that is sufficientlywater-insoluble to form a separate oil phase resistant to waterdispersion, said method comprising preparing a soil treating concentratecomposition having from about 4 to about 40 parts of an ethoxylated C₁₆-C₁₈ tertiary amine having 2-10 ethoxy groups per mol, from about 1 toabout 15 parts of at least one aliphatic carboxylic acid having fromabout 6 to about 12 carbon atoms; from about 1 to about 6 parts a C₇-C₁₂ aliphatic alcohol or mixture of such alcohols, from about 0 toabout 10 parts of a C₄ and lower alcohol, and the balance being water tocreate a total of about 100 parts by volume, dispersing said concentratecomposition in from about 10 to about 200 parts of water per part ofconcentrate, contacting said soil and said bacteria and said contaminanthydrocarbon fuel with said treating concentrate, permitting saidcomposition to disperse said hydrocarbon contaminants within said soiland, permitting said naturally occurring bacteria to attack theconstituents of said hydrocarbon spill, thereby degrading saidhydrocarbon into a reduced level of toxicity relative to said flora andsaid aquatic life characterizing said soil and water.
 2. A method asdefined in claim 1 which further includes adding additional water-bornebacteria to accelerate degradation of said fuel.
 3. A method ofdispersing spilled petroleum hydrocarbon materials to facilitate theirdegradation within a sewage system, said method comprising directlyadding to said spilled petroleum hydrocarbon materials at least duringthe time said material is entering and traversing a sewer system, a massof water having dispersed therein a concentrate comprising from about 4to about 40 parts of an ethoxylated C₁₆ -C₁₈ tertiary amine having 2-10ethoxy groups per mol, from about 1 to about 15 parts of at least onealiphatic carboxylic acid having from 6 to 12 carbon atoms; from about 1to about 6 parts a C₇ -C₁₂ aliphatic alcohol or a mixture of suchalcohols, from 0 to 10 parts of a C₄ and lower alcohol, and the balancebeing water to create a total of about 100 parts by volume, saidconcentrate being dispersed in said water in an amount of from about 0.5to about 10 parts per hundred parts of water.